Catalytic alkyne metathesis and stoichiometric metal-alkylidyne formation from NMo(OR)3 complexes promoted by Lewis acids

Nitride complex N Mo(OCMe2CF3)(3) is synthesized in 78% yield on a multigram scale. Although the irreversible but sluggish conversion of terminal molybdenumenitride complexes N Mo(OCMe(CF3)(2))(3) (1) and N Mo(OC(CF3)(3))(3)(NCMe) (2) to their propylidyne analogs EtC Mo(OR)(3)(DME) (OCMe(CF3)(2) (3), OC(CF3)(3) (4)) via metathesis with 3-hexyne occurs, the analogous reaction with N Mo(OR)(3) (OR] OCMe2CF3 (5), OCMe3 (6)) complexes does not occur under similar reaction conditions. However, the kinetic barrier to alkylidyne formation from 5 and 6 with internal alkynes can be overcome through the addition of simple Lewis acids, including MgBr2, MgI2 and BPh3 in specific instances. Although this typically leads to accelerated decomposition of the alkylidyne complex so formed, the combination of metalenitride complex plus exogenous Lewis acid frequently leads to alkyne metathesis of the test substrates 1-phenyl-1-propyne and 1-phenyl-1-butyne under milder conditions than possible in the absence of Lewis acid, in some cases at room temperature. The interaction of solvent, ancillary alkoxide ligands, and Lewis acid is complex and was not predicted a priori. New benzylidyne complexes 4-MeOC6H4C Mo(OC(CF3)(3))(3)(MeOC6H4CN) (22%), 4-PheC(6)H(4)C Mo(OC(CF3)(3))(3)(4-PhC6H4CN) (46%) were isolated in low yield via the nitride-to-alkylidyne route upon reaction with suitable diarylalkynes. Several related alkylidyne complexes were formed but could not be separated cleanly from the alkyne reagents used. (C) 2012 Published by Elsevier B.V.